Halogenated alkenyl succinic anhydride-amine reaction product

ABSTRACT

A reaction product of detergent-dispersant properties in lubricating oil prepared by the sequential method of (1) reacting polyalkene of from 30 to 300 carbons with maleic anhydride to form alkenyl succinic anhydride, (2) contacting the alkenyl succinic anhydride with chlorine or bromine in the absence of hydroxylic and solvent compounds to form halogenated alkenyl succinic anhydride, (3) contacting the halogenated alkenyl succinic anhydride with alkylene polyamine to form crude reaction product of halogenated alkenyl succinic anhydride and alkylene polyamine and (4) preferably contacting the crude reaction product with a strong inorganic base and recovering the purified reaction product. Lubricant compositions containing a detergentdispersant quantity of said halogenated succinic anhydridealkylene polyamine reaction product.

United States Patent 1191 Cullen et al.

[451 Feb. 4, 1975 1 HALOGENATED ALKENYL SUCCINIC ANl'lYDRlDE-AMINE REACTION PRODUCT [75] Inventors: William P. Cullen, Fishkill; Harry Chafetz, Poughkeepsie, both of NY.

[73] Assignee: Texaco Inc., New York, NY.

[22] Filed: July 9, 1973 [21] Appl. No.: 377,473

[52] 11.8. Cl 252/5l.5 A, 260/3265 F [51] Int. Cl Cl0m H36 [58] Field of Search 252/515 A [56] References Cited UNITED STATES PATENTS 3,215,707 11/1965 Rense 252/515 A X 3,219,666 11/1965 Norman et al 252/515 A X 3,374,174 3/1968 Le Suer 252/5l.5 A X 3,620,977 11/1971 Honnen et al. 252/515 A Primary ExaminerW. Cannon Attorney, Agent, or Firm-T. H. Whaley; C. G. Ries [57] ABSTRACT A reaction product of detergent-dispersant properties in lubricating oil prepared by the sequential method of (1) reacting polyalkene of from 30 to 300 carbons with maleic anhydride to form alkenyl succinic anhydride, (2) contacting the alkenyl succinic anhydride with chlorine or bromine in the absence of hydroxylic and solvent compounds to form halogenated alkenyl succinic anhydride, (3) contacting the halogenated alkenyl succinic anhydride with alkylene polyamine to form crude reaction product of halogenated alkenyl succinic anhydride and alkylene polyamine and (4) preferably contacting the crude reaction product with a strong inorganic base and recovering the purified reaction product. Lubricant compositions containing a detergent-dispersant quantity of said halogenated succinic anhydride-alkylene polyamine reaction product.

6 Claims, No Drawings '1 HALOGENATED ALKENYL SU'CCINIC ANHYDRIDE-AMINE REACTION PRODUCT BACKGROUND OF INVENTION An effective class of detergent-dispersa'nts for lubricating oil taught in the prior art are the N-substituted alkenyl succinimides characterized by theformula:

where R is alkenyl (monovalent, monoolefmic aliphatic hydrocarbon radical) of from to 300 carbons and D is an amine radical selected from the group consisting of alkylene amino and polyalkylene polyamine. These prior nitrogenous dispcrsants are prepared by reacting polyalkene or halogenated polyalkene with maleic anhydride to form the alkenyl succinic anhydride followed by the direct reaction of the succinic anhydride with alkylene diamine or polyalkylene polyamine. The prior art succinimides. although effective detergentdispersants are finding increasing difficulty in meeting the present day and future requirements in regard to preventing or inhibiting the formation of varnish in automotive engines.

In one effort to meet this varnish problem, the prior art. as represented by U.S. Pat. No. 3,620,977. developed a reaction product of halogenated succinyl lactone and a hydrocarbon amine by contacting alkenyl succinic anhydride with a halogen in the presence of hydroxylic compound such as water and methanol to form a halogenated succinyl lactone and then reacting this lactone with hydrocarbon amine to form a complex nitrogenous reaction product which is then subjected to a solvent extraction, e.g., methanol extraction to remove the undesired by-products. In the product defining procedure of the prior art, the hydroxylic compound is indicated to be essential.

DESCRIPTION OF THE INVENTION We have discovered and this constitutes our invention a novel detergent-dispersant reaction product CH n 2 R-CH -C-CH which inhibits or prevents the formation of varnish in automotive engines, lubricant compositions thereof, a method of preparation of improved economics and lubricating compositions thereof. More specifically, we

- ca c have discovered a varnish inhibiting detergentdispersant and lubricant compositions thereof which is prepared by a novel process which has the improved economics of omittingsolvent and the employment of hydroxylic compounds and further has the improved feature of employing a relatively inexpensive inorganic base as a final step for product quality enhancements as opposed to the more costly liquid solvent treatments of the prior art.

Broadly, thenovel detergent-dispersant is a reaction product of the halogenated alkenyl succinic anhydride and alkylene polyamine. In actuality, it is a complex mixture of many individual compounds, and therefore. is necessarily defined in terms of manufacturing medi al..-

Hereinbefore and hereinafter the terms *halogen and halogenated within the meaning of this invention are limited to chlorine and bromine.

In the first stage of the product defining procedure, alkenyl succinic anhydride of the formula:

RTiETt i s a monov alent, monoolefinic polyalkene radical-(alkenyl) of between about 30 and 300 carbon atoms and oil solubilizing in nature is contacted with halogen gas selected from the group consisting ofchlorine or bromine at a temperature between about and 150C. under a pressure of between about atmospheric and psig utilizing a mole ratio of anhydride to halogen of between about 110.5 and l:2, the halogen introduction being normally continued until the resultant halogenated succinic anhydride has a halogen content of between about 1.5 and 5.0 wt. usually representing a reaction time of between about 2 and 8 hours. Halogenation conditions forming essentially a monohalogenated alkenyl succinic anhydride are the most preferred. Some of the principal reactions in the first stage can be characterized by the following equations assuming chlorine and polyisobutylene succinic anhydride reactants and an unreacted polyisobutylene carry over from the anhydride preparation:

R-CH=C ca -ca c CH CH -E sentially complete removal of volatile by-products such as hydrogen chloride. it is to be noted that one of the essential features of this stage is that it is conducted in the absence of hydroxylic solvent and under neat conditions, that is, in the absence of inert solvent.

In the second stage of the product defining procedure, the crude or purified halogenated alkenyl succinic anhydride prepared in the first stage is contacted with an alkylene polyamine characterized by where is an integer of from 1 to 6, v is an integer of from 2 to 6. and z is an integer of from to 4, at a temperature between about 100 and 200C. utilizing a mole ratio of halogenated succinic anhydride intermediate to alkylene polyamine of between about 1:1 and lzlO to form the halogenated succinic anhydridealkylene polyamine reaction product. The amination as in the first stage halogenation is conducted in the absence of added solvent and in the absence of added hydroxylic compounds. This absence not only characterizes the chemical nature of the final products formed but contribute to the economy of the process through the savings afforded by the non need of solvent and hyvia filtration, followed by removal of the inert solvent. volatile amines and residual hydrogen halides via stripping with inert gas leaving the purified mixture of reaction product of halogenated alkenyl succinic anhydride and alkylene polyamine.

In respect to the alkenyl group, as heretofore stated, it represents a monovalent monoolefinic polyalkene radical of between about 30 and 300 carbon. Specific examples of alkenyl contemplated herein are polyethylene, polypropylene, polybutylene and polyisobutylene radicals and monovalent radicals of copolymers of alkenes such as copolymer of ethylene and propylene and the copolymer of propylene and butylene. Most preferably, the alkenyl group is of a molecular weight between about 900 and 2000 and a specific example of the most preferred is polyisobutylene. particularly of a molecular weight of about l250.

illustrative alkylene polyamine reactants contemplated herein include ethylene diamine, propylene diamine, hexamethylene diamine, diethylene triamine, and pentaethylene hexamine.

Examples of base materials for third stage utilization are sodium hydroxide, potassium hydroxide, barium oxide, calcium oxide, sodium carbonate, potassium droxylic compound and the cost involved in their sepacarbonate, calcium carbonate, and barium carbonate ration from the crude product. with sodium hydroxide being the preferred material Some of the principal reactions in the second stage basis cost and effectiveness. can be characterized by the following equations In the foregoing procedure, the absence of hydroxwherein the reactants are ethylene diamine and crude ylic compound is critical in regard to the chemical polyisobutylene succinic anhydride. structure of the intermediate and final products in that "7 H V V m V 7.... fiv z 9H -C1 IH NHCH CH NH R-CH -C=CH R-CH -C=CH ll 1 ll R-CH-C-CH -CH C R-CH-C-CH CH-C,

n 2 i +H NCH OH NH n 2 N 2 2 2 Cl- CH CH C NH CH CH C 2 H I II 0 CI-I CH NH O O 0 n n R-CH=CCH -CH C R--CH=CCH CH--C v 0 6NCH CH NH CH CH -.8 CH CH O 0 In addition to the isomers shown other double bondiso mers are also present.

The crude aminated reaction product can be purified by stripping off the volatile materials via inert gas blowing followed by standard filtration techniques through materials such as diatomaceous earth. However, in one embodiment of the invention the crude reaction product is diluted with an inert solvent such as liquid alkane of from 5 to 12 carbons, e.g., hexane, isooctane, whereupon an inorganic base such as alkali metal hydroxide, alkaline earth metal oxide, alkali metal carbonate and alkaline earth metal carbonate is introduced therein. The base contact with the diluted reaction product is conducted at a temperature between about 20 and lC. utilizing a ratio of gram atoms of halogen in the halogenated alkenyl succinic anhydride to equivalents of inorganic base of between about 1:1 and 1:2. At the end of the inorganic base treatment, the treated mixture components are separated by standard means, e.g.,

the prese ii c e of hydroxylic compounds of the prior art direct the reaction to form succinyl lactone materials rather than the non-lactone succinic anhydrides produced in the subject product defining method. The absence of hydroxylic compound not only produces a product of equal varnish removing ability of the prior art product, but has the added advantage of reducing the cost of additive since the cost of hydroxylic compound and necessary separation are not encountered in the subject product defining process.

A second important feature of the invention is the use of the discovery that the products could be successfully purified utilizing a relatively inexpensive inorganic base rather than the complex and costly methanol extraction which was previously believed to be necessary to maximize the effectiveness of the nitrogenous succinyl dispersant.

The lubricant compositions of the invention comprise a major amount of hydrocarbon oil of lubricating viscosity and a detergent-dispersant amount of the aforedescribed halogenated succinic anhydridealkylene polyamine reaction product. Advantageously, in the finished lubricating oil compositions, the reaction product content ranges between about 0.1 and wt. preferably between about 0.5 and 5 wt. 1n the lubricating oil concentrates from which the finished lubricating compositions are derived via the addition of added lubricating oil, reaction product contents between about 10 and 50 wt. are found.

The hydrocarbon oil in the finished lubricating compositions advantageously constitutes at least about 85 wt. preferably between about 90 and 98 wt. and in the lube oil concentrates between about 50 and 90 wt. 7c. It is to be noted that even in the lubricating oil concentrates the reaction product exhibits detergentdispersancy as well as varnish inhibition.

Examples of the hydrocarbon base oils contemplated herein are the naphthenic base, paraffinic base and mixed base mineral oils, lubricating oils derived from coal products and synthetic bils, e.g., alkylene polymers such as polypropylene and polyisobutylene of a molecular weight of between about 250 and 2500. Advantageously, a lubricating base oil having a lubricating oil viscosity at 100F. of between 50 and 2000, preferably between about 100 and 600, are normally employed for the lubricant compositions and concentrates thereof. (SUS basis) In the contempiated finished lubricating oil composi- ,tions other additives may be included in addition to the nitrogenous dispersant of the invention. These additives may be any of the suitable standard pour depressants, viscosity index improvers, oxidation and corrosion inhibitors, anti-foamants, supplementary detergent-dispersants, etc. Exactly what additional additives are included in the finished oils and the particular amounts thereof will depend on the particular use and conditions desired for the finished oil product.

Specific examples of the supplementary additives are as follows:

A widely used and suitable V1 improver is the polymethacrylate having the general formula:

where R is an aliphatic radical of from 1 to 2 0 carbons and n is an integer of between about 600 and 35,000. One of the most suitable V1 improvers is the tetrapolymer of butyl methacrylate, dodecyl methacrylate, octadecyl methacrylate and dimethylaminoethyl methacrylate having a respective component weight ratio in the polymer of about 4:l0:5.l. The V1 improvers are normally employed in the finished lubricant compositions in quantities between about 0 and 10 wt.

One of the commonly employed lube oil corrosion inhibitors are antioxidants of the divalent dialkyl dithiophosphates resulting from the neutralization of a P S -alcohol reaction product with a divalent metal or divalent metal oxide. Barium and zinc and dialkyl diand 2,2'-diethyl-4-p-octyldiphenylamine. The corrosion and oxidation inhibitors are usually present in the finished lubricating oil composition in concentrations of between about 0.1 and 3 wt.

Examples of supplementary detergent-dispersants which can be employed are the monoethoxylated inorganic phosphorus acid free, steam hydrolyzed polyalky1ene(500-50,000 M.w.)-P S reaction product, alkaline earth metal alkylphenolates such as barium nonyl- 10 phenolate, barium dodecylcresolate, calcium dodecylphenolate and the calcium carbonate overbased calcium alkaryl sulfonates formed by blowing a mixture of calcium hydroxide and calcium alkaryl sulfonate, e.g., calcium alkylbenzene sulfonate of about 900 m.w. with carbon dioxide to form a product having a total base number (TBN) of 50 or more, e.g., 300 to 400.

1f antifoamants are employed in the finished compositions, one widely used class which is suitable are the. dimethyl silicone polymers employed in amounts of between about 10 and 1000 ppm.

The following examples will further illustrate the product, compositions and method of the invention but are not to be construed as limitations thereof.

EXAM PLE 1 This example illustrates the novel dispersant reaction products of the invention and their method of preparation.

1 First Stage To a 5 liter 3-necked flask fitted with a stirrer, con-' denser, sodium hydroxide scrubber, glass inlet tube.

thermowell and thermocouple there was charged 3600 grams 1.5 mole based on Sap. No.) of polyisobutylene. (*1250 m.w.) succinic anhydride. Stirring was initiated and the polyisobutylene succinic anhydride was heated to a temperature of 125C. whereupon chlorine gas was passed therethrough at a rate of about 500m1s. per minute for a period of about 2.5 hours and until a 40 net weight increase of 90 grams was obtained. The

product was blown with nitrogen at a temperature of about 125C. at a rate of about 500 m1s./minute for a period of about 30 minutes and until detectible evolution of hydrogen chloride and chlorine gas had ceased.

The product was analyzed and determined to have a chlorine content of 2.2 wt: containing as one principal product monochlorinate polyisobutylene (-1250 m.w.) succinic anhydride.

Second Stage To a 12 liter 3-necked flask fitted with a stirrer, condenser, gas inlet tube, thermowell and thermocouple there were charged 4700 grams (3.4 moles) of the chlorinated succinic anhydride intermediate mixture prepared in the first stage and 600 grams (10.0 moles) of ethylene diamine. The flask was heated to reflux ==125C.) for about 8 hours. At the end of the 8 hour period the reaction mixture was dissolved in 5 liters of heptane and the heptane solution was treated with 1 36 grams of powdered sodium hydroxide under conditions then filtered through diatomaceous earth and the heptane solution was stripped off under reduced pressure to a temperature of C. affording a clear product reaction mixture which upon analysis was found to have a nitrogen content of 1.5 wt. a chlorine content of 0.9 wt. and a sodium content of ppm.

This example illustrates the material difference in the hydroxylic compound free procedure of the invention and the prior art procedure employing solvent and hydroxylic compound.

The procedure of the first stage of Example I was repeated and the recovered chlorinated polyisobutylene (l250 m.w.) succinic anhydride containing reaction product was designated as Product A and set aside.

in the comparative procedure in a 2000 mls. flask as described in Example I there was charged 675 grams of polyisobutenyl (1250 m.w.) succinyl anhydride, 250 mls. of benzene and 44 mls. of methanol. The reaction mixture was heated to 50C. and chlorine was bubbled through the reaction mixture for a period of 2 hours until a weight increase of approximately 21 grams was attained. The reaction mixture was blown with nitrogen at 50C. for a period of 1 hour. Benzene and water were then removed at a temperature of IC. at a pressure of I00 mm Hg. Analysis of the resultant product was found to have a chlorine content of 2.96 71. The product was designated as Product B.

Products A and B were subjected to infrared spectral analysis and Product A was found to have no change in carbonyl absorption over the non chlorinated polyisobutenyl l 250 m.w.) succinic anhydride. However, in the case of Product B chlorinated in the presence of methanol the spectral data indicated the presence of methyl ester of an acid lactone and free carboxyl radicals also present.

EXAMPLE II! This example illustrates the lubricating oil compositions of the invention and the effectiveness of the reaction products of the invention as dispersants and varnish formation inhibitors.

The following tests were employed as measure of the dispersancy and varnish inhibiting effect of the lubricant compositions.

Bench Sludge Test (BST) This test measure the relative dispersancy oflubricating oil compositions. in the Bench Sludge Test the oil compositions containing particular solid matter and engine blow-by agitated to evenly disperse the particulate matter throughout the oil. After centrifuge the depth of sediment is compared against a standard to show the effect of the dispersant. Sediment depths less than 1 mm indicate good dispersancy.

Bench Varnish Test (BVT) This test is also a measure of relative dispersancy of lubricating oil compositions.

In the Bench Varnish Test a mixture containing the test oil and a diluent are heated at an elevated temperature. After heating, the turbidity of the resultant mixture is measured. A low 72 turbidity (()-l 0) are indicative of good dispersancy while high results (-100) are indicative of oils of increasingly poor dispersancy.

Two fully formulated SAE Grade 30 lubricants were tested, namely, representative Composition C containing the chlorinated polyisobutenyl succinic anhydrideethylene diamine reaction product of Example I and comparative control Composition D identical to Composition C exdept the reaction product off Example I is omitted. The Formulation C was blended so as to have a dispersant nitrogen content of 0.06 wt. a calcium content of 0.23 wt. and a zinc content of 0.12 wt. Comparative Formulation D was also of the same blend except there was no nitrogen containing 'component, and therefore, no nitrogen content. Compositions of the formulations tested are as follows:

"Alkyl is a mixture of isopropyl and C, alcohols Derhed from 4:] wt. mixture of lauryl to stearyl melhacrylale monomer.

The above two compositions were tested in the aforedescribed dispersancy tests with the following results:

Composition BST BVT C 0.2 2.5 D L6 EXAMPLE IV This example further illustrates the lubricating oil compositions of the invention and the effectiveness of the halogenated alkenyl succinic anhydride-alkylene polyamine reaction products of the invention as dispersants and varnish inhibitors in lubricating oils.

The dispersant tests employed are described as follows M SC V Test This test is the Ford Sequence VC Test and is detailed in Multicylinder Test Sequence for Evaluating Automotive Engine Oils ASTM Special Technical Publication under 3l5-E. This procedure is used to evaluate crankcase motor oils with respect to sludge and varnish deposits as well as their ability to keep the positive crankcase ventilation (PCV) valve clean and functioning properly. Ratings of 0 to 10 are given, 10 representing absolutely clean and 0 rating representing heavy sludge and varnish deposits and a clogged PCV valve.

MS [I C Test This is a light duty engine test for determination of the ability of automotive engine oil to prevent deposits forming on the PCV valve. The test operates utilizing an alternating cold and hot cycle. A 302 cubic inch engine is employed operating under the following conditions:

Performance of the oil is based upon the sludge deposits on the PVC valve, a rating of 10 representing clean and a rating of 0 representing heavily clogged.

L-38 Test This test is described in detail in the Federal Test Methods Standard (FTMS) No. 791a, Method 3405.

The purpose of this test is a method of determining the oxidation and copper lead bearing corrosion characteristics of crankcase oils. The perfomance of the test oil is judged by the weight loss of the copper lead bearing, the greater the bearing weight loss the poorer the anticorrosive ability of the crankcase oil.

Caterpillar l-H Test This test is described in detail in FTMS-791b-346.1. The purpose of this test is to evaluate the diesel detergent-dispersant characteristics and antiwear properties of diesel crankcase oils under high speed and medium supercharge test conditions. The engine employed is a 1Y73 single engine Caterpillers diesel lubricant test engine. The perfomance of the test lubricant is judged by examination of the power section for ring sticking, piston deposits and ring, piston and liner wear. Satisfactory performance requires not more than 30 vol. of the top groove filing (TGF) filled with deposits and not more than 50% of the second groove covered with lacquer and the piston below the second groove should be essentially clean with no ring sticking.

A fully formulated SAE Grade 30 lubricant composition was tested, namely, representative Composition E containing the nitrogenous reaction dispersant of Example type of 1.6 wt. nitrogen and 0.48 wt. chlorine content. The formulation was blended to have a dispersant nitrogen content of 0.06 wt. nitrogen, a calcium content of 0.23 wt. a zinc content of 0.15 wt. Composition of the formulation tested is as follows:

TABLE Ill lngredients. Weight 7: E

Mineral Oil (54 SUS at 100F.)

Zinc Dialkyl Dithiophosphate* Overbased Calcium Alkaryl Sulfonate (900 m.w. 300+ TBN) Polyalkylmethacrylate** Dispersant of Ex. I type The above composition was tested in the aforedescribed dispersancy test with the following results:

TABLE 111 Rating 5 Tests E 3 Clean As can be seen from the foregoing, the complex nitrogenous dispersant is a very effective dispersant for 6 both moderate temperature gasoline engine and high temperature diesel engine operation.

We claim;

l. A lubricating oil composition comprising a major amount of a hydrocarbon oil of lubricating viscosity and between about 0.1 and 50 wt. ofa reaction product of halogenated alkenyl succinic anhydride and alkylene polyamin e prepared by the method comprising reacting under neat conditions, i.e. in the absence of either hydroxylic solvent or inert solvent. an alkenyl succinic anhydride characterized by the formula:

where R is a monoolefinic, monovalent polyalkene radical of from 30 to 300 carbons with a halogen selected from the group consisting of chlorine and bromine at a temperature between about 50 and 150C. utilizing a mole ratio of alkenyl succinic anhydride to said halogen of between about 110.5 and 1:2 to form a monohaloalkenyl succinic anhydride containing intermediate. contacting under neat conditions, i.e. in the absence of either hydroxylic solvent or inert solvent, said intermediate with an alkylene polyamine of the formula:

where x is an integer of from 1 to 6, y is an integer from 2 to 6 and z is an integer from 0 to 4 at a temperature between about and 200C. utilizing a mole ratio of said intermediate to alkylene polyamine of between about 1:1 and 1:10 to form said halogenated alkenyl succinic anhydride alkylene polyamine reaction product.

2. A lubricating oil composition containing a major amount of a hydrocarbon oil of lubricating viscosity and between about 0.1 and 50 wt. 7( of a base treated reaction product of halogenated alkenyl succinic anhydride and alkylene polyamine prepared by the method comprising reacting under neat conditions, i.e. in the absence of either hydroxylic solvent or inert solvent, an alkenyl succinic anhydride characterized by the formula:

where R is a monoolefinic, monovalent polyalkene radical of from 30 to 300 carbons with a halogen selected from the group consisting of chlorine and bromine at a temperature between about 50 and C. utilizing a mole ratio of alkenyl succinic anhydride to halogen of between about 120.5 and 1:2 to form a halogenated alkenyl succinic anhydride containing intermediate, contacting under neat conditions, i.e. in the absence of either hydroxylic solvent or inert solvent, said intermediate with an alkylene polyamine of the formula:

H N+CH2-),l-NH-(-CH ),NH -l-,-(CH -)-,NH

where x is an integer from I to 6, y is an integer from 2 to 6 and z is an integer from m 4 at a temperature between about 100 and 200C. utilizing a mole ratio of said intermediate to alkylene polyamine of between about 1:] and l:l0 to form said halogenated alkenyl succinic anhydride-alkylene polyamine reaction product, and contacting said product with a base selected from the group consisting of alkali metal hydroxide, alkaline earth metal oxide, alkali metal carbonate and alkaline earth metal carbonate at a temperature between about 20 and 150C. utilizing a ratio of gram atoms of halogen in said halogenated alkyl succinic anhydride to equivalents of said base of between about [:1 and 1:2 and recovering said base treated halogenated alkenyl succinic anhydride reaction product from the base treated mixture.

3. A lubrication oil composition in accordance with claim 1 wherein said R is polyisobutylene. said halogen is chlorine, and said alkylene polyamine is ethylene diamine and said base is sodium hydroxide.

4. A lubricating oil composition in accordance with claim 2 wherein said R is polyisobutylene. said halogen is chlorine, said alkylene polyamine is ethylene diamine and said base is sodium hydroxide.

5. A lubricating oil composition in accordance with calim 1 containing between about 0.1 and 10 wt. 72 of said reaction product.

6. A lubricating oil composition in accordance with claim 2 containing between about 0.l and 10 wt. 71 of said base treated reaction product. k l 

2. A lubricating oil composition containing a major amount of a hydrocarbon oil of lubricating viscosity and between about 0.1 and 50 wt. % of a base treated reaction product of halogenated alkenyl succinic anhydride and alkylene polyamine prepared by the method comprising reacting under neat conditions, i.e. in the absence of either hydroxylic solvent or inert solvent, an alkenyl succinic anhydride characterized by the formula:
 3. A lubrication oil composition in accordance with claim 1 wherein said R is polyisobutylene, said halogen is chlorine, and said alkylene polyamine is ethylene diamine and said base is sodium hydroxide.
 4. A lubricating oil composition in accordance with claim 2 wherein said R is polyisobutylene, said halogen is chlorine, said alkylene polyamine is ethylene diamine and said base is sodium hydroxide.
 5. A lubricating oil composition in accordance with calim 1 containing between about 0.1 and 10 wt. % of said reaction product.
 6. A lubricating oil composition in accordance with claim 2 containing between about 0.1 and 10 wt. % of said base treated reaction product. 